CN115074753A - Post-treatment impurity removal method for electrolytic manganese dioxide for alkaline manganese battery - Google Patents
Post-treatment impurity removal method for electrolytic manganese dioxide for alkaline manganese battery Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000012535 impurity Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 37
- 239000011572 manganese Substances 0.000 title claims abstract description 37
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 112
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000003513 alkali Substances 0.000 claims abstract description 47
- 239000012043 crude product Substances 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 35
- 239000000047 product Substances 0.000 claims abstract description 25
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 15
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 11
- 239000011028 pyrite Substances 0.000 claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- 238000010298 pulverizing process Methods 0.000 claims abstract description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 17
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 16
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 229940099596 manganese sulfate Drugs 0.000 claims description 14
- 235000007079 manganese sulphate Nutrition 0.000 claims description 14
- 239000011702 manganese sulphate Substances 0.000 claims description 14
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 7
- 239000011733 molybdenum Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 description 16
- 238000000227 grinding Methods 0.000 description 9
- 238000005086 pumping Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 230000005484 gravity Effects 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/21—Manganese oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a post-treatment impurity removal method of electrolytic manganese dioxide for an alkaline manganese battery, which comprises the steps of mixing manganese ore powder, pyrite and dilute sulfuric acid for reaction leaching, and obtaining a crude product of electrolytic manganese dioxide after purification and electrolysis treatment; the method for post-treating and removing impurities of crude manganese dioxide comprises the following steps: (1) and (3) rinsing the crude product for the first time: firstly, rinsing the crude electrolytic manganese dioxide with hot water at the temperature of 75-95 ℃ for multiple times, and rinsing for one section until the mass concentration of sulfuric acid in a water sample is less than 0.1%; (2) and (4) second-stage rinsing: taking alkali liquor as neutralization solution and adding hydrogen peroxide solution to carry out cyclic neutralization reaction for multiple times, and carrying out two-stage rinsing on the crude manganese dioxide, wherein the neutralization reaction time is 3-8 h/time, the neutralization temperature is 75-95 ℃, and the neutralization reaction is rinsed until the pH value of the crude manganese dioxide is 5-7; (3) pulverizing, removing impurities, and mixing to obtain the final product. The method of the invention carries out post-treatment and impurity removal on the crude manganese dioxide, so that the content of molybdenum which is a very harmful impurity in the product is reduced to be within 0.5ppm, and the requirement of high-end users of high-performance alkaline batteries can be met.
Description
Technical Field
The invention relates to the technical field of alkaline battery raw material processing, in particular to a post-treatment impurity removal method for electrolytic manganese dioxide for an alkaline manganese battery.
Background
The alkaline manganese cell as high power cell with optimal performance-price ratio in cell industry has the characteristics of stable working voltage, continuous discharge of large current, excellent performance, long storage time (up to 3-5 years), good low-temperature performance and leakage-proof performance, and the like, and is popular with consumers at home and abroad. The mercury-free alkaline manganese type electrolytic manganese dioxide, which is a main raw material required for producing the alkaline manganese battery, has the global consumption of over 30 ten thousand tons every year, increases by more than 10 percent every year, and has wide market prospect.
The chemical purity of the major manganese dioxide content of the high performance alkaline manganese battery positive electrode material EMD (electrolytic manganese dioxide) has a significant impact on the discharge and storage performance of the battery. The chemical purity of the product is determined mainly by the electrolytic manganese dioxide used as the raw material. The general alkaline battery EMD product can be directly used as the anode material of a primary alkaline zinc-manganese battery, but the content of molybdenum as a harmful impurity of the anode is too high, so that the requirement of the high-performance alkaline battery EMD is not met. Namely, the alkaline battery EMD product produced by the prior art process has too high molybdenum content to be used as the anode material of the high-performance alkaline battery. The market situation of alkaline batteries, particularly high-performance alkaline batteries, which are more in market demand at present, is developing in the daytime, and the market is rapidly rising, so that research and development of the technology are carried out.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a method for post-treating and removing impurities from electrolytic manganese dioxide for an alkaline manganese battery, so as to overcome the defects that the electrolytic manganese dioxide has high molybdenum content and cannot be used as a high-performance alkaline battery material.
In order to realize the purpose, the invention provides a post-treatment impurity removal method of electrolytic manganese dioxide for an alkaline manganese battery, manganese ore powder, pyrite and dilute sulfuric acid are mixed, reacted and leached, and a crude electrolytic manganese dioxide product is obtained after purification and electrolysis treatment; the method for post-treatment impurity removal of crude manganese dioxide comprises the following steps:
(1) and (3) rinsing the crude product for the first time: firstly, rinsing the crude electrolytic manganese dioxide with hot water at the temperature of 75-95 ℃ for multiple times, and rinsing for one section until the mass concentration of sulfuric acid in a water sample is less than 0.1%;
(2) and (4) second-stage rinsing: taking alkali liquor as neutralization solution and adding hydrogen peroxide solution to carry out cyclic neutralization reaction for multiple times, and carrying out two-stage rinsing on the crude manganese dioxide, wherein the neutralization reaction time is 3-8 h/time, the neutralization temperature is 75-95 ℃, and the neutralization reaction is rinsed until the pH value of the crude manganese dioxide is 5-7;
(3) pulverizing, removing impurities, and mixing to obtain the final product.
Preferably, in the above technical scheme, the first rinsing step (1) is:
1) acid washing for the first time: after adding the crude product and hot water into a rinsing barrel, circulating the water in the barrel from bottom to top by using a pump for 1-5 hours, and draining;
2) performing secondary acid washing, namely after hot water is fed into a rinsing barrel, circulating the water in the barrel up and down by using a pump for 1-5 hours, detecting the sulfuric acid content of a water sample, and draining;
3) and (3) if the mass concentration of the sulfuric acid in the water sample is more than or equal to 1%, continuously repeating the acid washing in the step 2) until the mass concentration of the sulfuric acid in the water sample is less than 1%, and performing the following steps.
Preferably, in the above technical scheme, the alkali solution is a sodium bicarbonate solution, and the mass concentration is 1-10%.
Preferably, in the above technical solution, in the second rinsing in step (2), the concentration of the hydrogen peroxide solution is 50-500 ppm.
Preferably, in the above technical solution, the second rinsing step in step (2) is:
1) and (3) first circulation: adding alkali liquor and hydrogen peroxide solution into a rinsing barrel, controlling the temperature of the solution to be 75-95 ℃, circulating under the alkali liquor in the barrel by using a pump for 2-4 hours, then soaking for 0.5-2 hours, and taking a water sample to detect the concentration of the alkali liquor;
2) and (3) second circulation: adding alkali liquor and (fed-batch) hydrogen peroxide solution into a rinsing barrel, controlling the solution temperature at 75-95 ℃, circulating the solution under the alkali liquor in the barrel for 2-4h by using a pump, then soaking for 0.5-2h, and taking a water sample to detect the concentration of the alkali liquor;
3) taking the crude manganese dioxide, determining that the pH value reaches 5-7, and stopping circulating alkali washing; if not, continuing to cycle step 2).
Preferably, in the above technical scheme, after the neutralization and rinsing in step 3), a proper amount of alkali is supplemented or neutralized with acid water according to the size of the pH value of the crude product and the concentration of sodium bicarbonate in the alkali circulation liquid until the pH value is qualified, and after the water is drained cleanly, the rinsing is finished.
Preferably, in the above technical solution, the leaching is: mixing and reacting manganese ore powder, pyrite powder and dilute sulfuric acid at the temperature of 90-100 ℃, the pH value of a reaction solution is 1-3.5, and the reaction time is 3-6h, wherein the mixing ratio of the manganese ore powder, the pyrite powder and the dilute sulfuric acid is 1-5: 1: 1-5, and the liquid-solid ratio is 8-20: 1.
Preferably, in the above technical solution, the purifying is: adding calcium carbonate into the manganese sulfate solution obtained by leaching, adjusting the pH value of the solution to 3-7, keeping the solution at the temperature of 30-80 ℃ for 0.5-3h, then adding barium sulfide, keeping the solution for 0.5-3h, and performing solid-liquid separation by pressure filtration to obtain the manganese sulfate solution without impurity ions, wherein the impurity ions are qualitative ions without iron and copper.
Preferably, in the above technical scheme, the manganese sulfate solution is sent to an electrolytic cell for electrolysis to obtain a crude product of the electrolyte IIManganese oxide; the electrolysis conditions were: the concentration of manganese sulfate solution is 0.5-0.7mol/L, and the current density is 50-120A/m 2 The concentration of the sulfuric acid in the electrolyte is 0.5-0.6mol/L, and the electrolysis period is 8-12 days.
Preferably, in the above technical scheme, the powdered manganese dioxide powder is rinsed in hot water at a temperature of 75-95 ℃, and impurity iron brought in during the grinding is deeply removed.
Compared with the prior art, the invention has the following beneficial effects:
(1) the electrolytic manganese dioxide post-treatment impurity removal method for the alkaline manganese battery, disclosed by the invention, is used for performing post-treatment impurity removal on crude manganese dioxide and deep molybdenum removal treatment, so that the extremely harmful impurity molybdenum in the prepared product is reduced to an extremely low level, and is only within 0.5ppm, and the requirements of high-end users of high-performance alkaline batteries can be met.
(2) The invention relates to a method for post-treating and removing impurities of electrolytic manganese dioxide for an alkaline manganese battery, which comprises the steps of carrying out post-treatment and impurity removal on a crude product of manganese dioxide, dividing rinsing of the post-treatment into two-stage rinsing, and keeping the main chemical content MnO of the manganese dioxide as much as possible 2 The water is not soaked by a large amount of strong alkali but enters a small amount of rinsing alkali liquor, and the second rinsing process is added, so that the water content is kept within 2 percent, the main content is up to 93-94 percent, and the problem of the main content is solved.
Drawings
FIG. 1 is a process flow diagram of a method for post-treatment impurity removal of crude manganese dioxide according to the present invention.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
As shown in fig. 1, a method for producing electrolytic manganese dioxide for an alkaline manganese battery according to an embodiment of the present invention comprises the following steps: manganese (ore) powder → pyrite sulfate chemical leaching → filter pressing 1 → purification → filter pressing 2 → aging → electrolysis → crude product → granule rinsing → deep impurity removal → secondary rinsing → powdering → gravity mixing → packaging and delivery. The prepared electrolytic manganese dioxide is used for producing the anode material of the high-performance alkaline battery.
The manganese (ore) powder is subjected to early-stage treatment to obtain a crude product, and the crude product is subjected to post-treatment for removing impurities. The main impurity removal production process of the electrolytic manganese dioxide post-treatment comprises the following steps of crude product → a section of rinsing barrel → acid washing → secondary rinsing → pH value adjustment → powder grinding → swing sieving → iron remover deironing → mixing in a mixing warehouse → packaging and delivery.
A post-treatment impurity removal method of electrolytic manganese dioxide for an alkaline manganese battery comprises the steps of mixing manganese ore powder, pyrite and dilute sulfuric acid, reacting and leaching, and obtaining a crude product of electrolytic manganese dioxide (END crude product) after purification and electrolysis treatment;
leaching: mixing and reacting manganese ore powder, pyrite powder and dilute sulfuric acid at the reaction temperature of 95 ℃, the pH value of a reaction solution is 2.5, and the reaction time is 4 hours, wherein the mixing ratio of the manganese ore powder, the pyrite powder and the dilute sulfuric acid is 3: 1: 2, the liquid-solid ratio is 10:1, and the mass concentration of the dilute sulfuric acid is 15%.
Purifying: synchronously purifying molybdenum, carrying out filter pressing on a manganese sulfate solution obtained after the combination reaction, adding calcium carbonate powder into the filter-pressed manganese sulfate solution, adjusting the pH value of the solution to 4, keeping the solution at 50 ℃ for 1 hour, then adding barium sulfide, and keeping the solution for 1 hour. And carrying out solid-liquid separation by filter pressing to obtain a manganese sulfate solution without impurity ions, wherein the impurity ions are qualitatively detected without iron and copper.
Electrolysis: carrying out filter pressing and aging on the purified manganese sulfate solution, and then sending the manganese sulfate solution to an electrolytic cell for electrolysis to obtain a crude product of electrolytic manganese dioxide; the electrolysis conditions were: the concentration of the manganese sulfate solution is 0.6mol/L, and the current density is 90A/m 2 The concentration of sulfuric acid in the electrolyte is 0.55mol/L, and the electrolysis period is 10 days. Obtaining the crude product (END crude product) of the electrolytic manganese dioxide index for the alkali manganese.
Example 1
The method for post-treating and removing impurities of the crude manganese dioxide prepared by the method comprises the following steps:
1. first-stage rinsing of crude product
1) Preparing materials: the hot water with the temperature of more than 80 ℃ is put into the feeding barrel, when the liquid level covers the conical bottom of the rinsing barrel, the crude product is hung into the rinsing barrel, and after the material is hung, the distance between the material level and the liquid level is lower than 30 cm.
2) Acid washing for the first time: adding the crude product and 90 deg.C hot water into a rinsing barrel, circulating the water in the barrel with a pump for 1 hr, stopping the circulating pump, discharging the washing acid solution (water temperature should be above 90 deg.C), and draining; (note: the feed water is not discharged outside, and the washing is filled with water for the first time).
3) Performing secondary acid washing, namely, after 90 ℃ hot water is fed into a rinsing barrel, circulating the water in the barrel up and down by using a pump for 2 hours, detecting the sulfuric acid content of a water sample, and draining;
3) thirdly, washing acid, namely, after 90 ℃ hot water is fed into a rinsing barrel, circulating the water in the barrel up and down by using a pump for 3 hours, detecting the sulfuric acid content of a water sample, and draining;
4) washing acid for the fourth time, namely, after 90 ℃ hot water is fed into a rinsing barrel, circulating the water in the barrel up and down by using a pump for 3 hours, detecting the sulfuric acid content of a water sample, and draining;
5) and (4) pickling until the mass concentration of sulfuric acid in the water sample is less than 1%, standing for 1 hour, and entering the next working procedure.
2. Two stage rinsing
1) Preparing materials: adding a proper amount of clear water into an alkali dissolving barrel, adding sodium bicarbonate into the alkali dissolving barrel, stirring and dissolving uniformly, then pumping into a rinsing barrel, circulating to make the solution uniform, pumping into the rinsing barrel to be neutralized, adding 300ppm hydrogen peroxide solution into the rinsing barrel, mixing the hydrogen peroxide solution in a flow adding manner, adding into the rinsing barrel, circulating to make the liquid level exceed the crude product by more than 30cm, and circulating well (if the alkali solution barrel is pumped completely, adding clear water to full), and starting circulation.
2) And (3) first circulation: controlling the temperature of the solution to be 90 ℃, circulating the solution under the alkali liquor in the barrel by using a pump for 3 hours, then soaking the solution for 1 hour, and taking a water sample to detect the concentration of the sodium bicarbonate solution.
3) And (3) second circulation: controlling the temperature of the solution at 90 ℃, circulating the solution under the alkali liquor in the barrel for 3 hours by using a pump, then soaking the solution for 1 hour, and taking a water sample to detect the concentration of the sodium bicarbonate solution.
4) And (3) third circulation: controlling the temperature at 90 ℃, circulating for 3 hours, sampling (crude product), measuring the pH value, wherein the pH value is 6, and the product is qualified (the pH value of the finished product is 5-7). If the product is not qualified, the circulation is continued (the temperature is controlled to be 75-95 ℃), and the pH value of the crude product and NaHCO in the alkali circulation liquid are determined 3 Adding sodium bicarbonate in appropriate amount until the pH value is qualified. And after the water is drained completely, finishing rinsing.
5) If the pH of the crude manganese dioxide is unqualified after the neutralization circulation, alkali is supplemented or acid water is used for reverse neutralization according to actual conditions, and the temperature is controlled at 90 ℃.
3. Powdering: electrolytic manganese dioxide was ground to 200 mesh powder using a Raymond mill.
4. Deeply removing impurities: rinsing the powdered manganese dioxide powder in hot water at the temperature of 90 ℃, and deeply removing impurity iron brought in during the grinding. When the powder is washed by hot water at 90 ℃, acid in the powder can be washed into water, and at the moment, the water is acidic and can dissolve the elemental iron, so that the iron removal effect of concentration is achieved.
5. And (5) mixing materials in a mixing bin by gravity to obtain a finished product, and packaging and leaving a factory.
The main indicators of the product obtained in this example are shown in table 1:
TABLE 1 product quality situation table
Example 2
The method for post-treating and removing impurities of the crude manganese dioxide prepared by the method comprises the following steps:
1. first-stage rinsing of crude product
Firstly, rinsing the crude electrolytic manganese dioxide with hot water at the temperature of 95 ℃ for multiple times, and rinsing the crude electrolytic manganese dioxide for one time until the mass concentration of sulfuric acid is less than 0.1%. The method comprises the following specific steps:
1) preparing materials: the hot water with the temperature of more than 80 ℃ is put into the feeding barrel, when the liquid level covers the conical bottom of the rinsing barrel, the crude product is hung into the rinsing barrel, and after the material is hung, the distance between the material level and the liquid level is lower than 30 cm.
2) Acid washing for the first time: adding the crude product and hot water at 95 ℃ into a rinsing barrel, circulating the water in the barrel upwards by using a pump for 1h, and draining;
3) performing secondary acid washing, namely circulating the water in the rinsing barrel under 95 ℃ by using a pump after the hot water is fed into the rinsing barrel for 5 hours, detecting the sulfuric acid content of a water sample, and draining;
4) thirdly, washing acid, namely, after 95 ℃ hot water is fed into a rinsing barrel, circulating the water in the barrel up and down by using a pump for 1 hour, detecting the sulfuric acid content of a water sample, and draining;
5) washing acid for the fourth time, namely, after 95 ℃ hot water is fed into a rinsing barrel, circulating the water in the barrel up and down by using a pump for 5 hours, detecting the sulfuric acid content of a water sample, and draining;
6) and (4) pickling until the mass concentration of sulfuric acid in the water sample is less than 1%, standing for 1 hour, and entering the next working procedure.
2. Two stage rinsing
1) Preparing materials: adding a proper amount of clear water into an alkali dissolving barrel, adding baking soda into the alkali dissolving barrel, stirring and dissolving uniformly, then pumping into a rinsing barrel, circulating to make the solution uniform, pumping into the rinsing barrel to be neutralized, adding 500ppm hydrogen peroxide solution into the rinsing barrel, mixing the hydrogen peroxide solution in a flow adding manner, adding into a circulating operation to make the liquid level exceed more than 30cm of the crude product, and circulating well (if the water in the alkali solution barrel is not full after the pump is finished, adding clear water to full), and starting circulation.
2) And (3) first circulation: controlling the temperature of the solution to be 95 ℃, circulating the solution under the alkali liquor in the barrel by using a pump for 1 hour, then soaking the solution for 1 hour, and taking a water sample to detect the concentration of the sodium bicarbonate solution.
3) And (3) second circulation: controlling the temperature of the solution to be 95 ℃, circulating the solution under the alkali liquor in the barrel by using a pump for 5 hours, then soaking the solution for 1 hour, and taking a water sample to detect the concentration of the sodium bicarbonate solution.
4) And (3) third circulation: controlling the temperature at 95 ℃, circulating for 1 hour, sampling (crude product), measuring the pH value, wherein the pH value is 5, and the product is qualified (the pH value of the finished product is 5-7). If the product is not qualified, the circulation is continued (the temperature is controlled to be 95 ℃), and the pH value of the crude product and NaHCO in the alkali circulation liquid are determined 3 Adding sodium bicarbonate in appropriate amount until the pH value is qualified. And after the water is drained completely, finishing rinsing.
5) If the pH of the crude manganese dioxide is unqualified after the neutralization circulation, alkali is supplemented or acid water is used for reverse neutralization according to actual conditions, and the temperature is controlled at 95 ℃.
3. Powdering: electrolytic manganese dioxide was ground to 200 mesh powder using a Raymond mill.
4. Deeply removing impurities: and rinsing the powdered manganese dioxide powder in hot water at the temperature of 95 ℃, and deeply removing impurity iron brought in during grinding. When the powder is washed by hot water at 95 ℃, acid in the powder is washed into water, and at the moment, the water is acidic and can dissolve simple substance iron, so that the iron removal effect of concentration is achieved.
5. And (5) mixing materials in a mixing bin by gravity to obtain a finished product, and packaging and leaving a factory.
The main indicators of the product obtained in this example are shown in table 1:
TABLE 1 product quality situation table
Example 3
The method for post-treating and removing impurities of the crude manganese dioxide prepared by the method comprises the following steps:
1. first-stage rinsing of crude product
Firstly, rinsing the crude electrolytic manganese dioxide with hot water at 75 ℃ for multiple times, and rinsing the crude electrolytic manganese dioxide for one time until the mass concentration of sulfuric acid is less than 0.1%. The method comprises the following specific steps:
1) preparing materials: hot water with the temperature of over 75 ℃ is put into the feeding barrel, when the liquid level covers the conical bottom of the rinsing barrel, the crude product is hung into the rinsing barrel, and after the material is hung, the distance between the material level and the liquid level is lower than 30 cm.
2) Acid washing for the first time: adding the crude product and 75 ℃ hot water into a rinsing barrel, circulating the water in the barrel up and down by using a pump, circulating for 5 hours, and draining;
3) performing secondary acid washing, namely, after 75 ℃ hot water is fed into a rinsing barrel, circulating the water in the barrel up and down by using a pump for 1 hour, detecting the sulfuric acid content of a water sample, and draining;
4) thirdly, washing acid, namely, after 75 ℃ hot water is fed into a rinsing barrel, circulating the water in the barrel up and down by using a pump for 5 hours, detecting the sulfuric acid content of a water sample, and draining;
5) washing acid for the fourth time, namely after 75 ℃ hot water is fed into a rinsing barrel, circulating the water in the barrel up and down by using a pump for 1 hour, detecting the sulfuric acid content of a water sample, and draining;
6) fifth washing acid, after 75 ℃ hot water is fed into the rinsing barrel, circulating the water in the barrel up and down by using a pump for 4 hours, detecting the sulfuric acid content of the water sample, and draining;
7) and (4) pickling until the mass concentration of sulfuric acid in the water sample is less than 1%, standing for 1 hour, and entering the next working procedure.
2. Two stage rinsing
1) Preparing materials: adding a proper amount of clear water into an alkali dissolving barrel, adding baking soda into the alkali dissolving barrel, stirring and dissolving uniformly, then pumping into a rinsing barrel, circulating to make the solution uniform, pumping into the rinsing barrel to be neutralized, adding 50ppm hydrogen peroxide solution into the rinsing barrel, mixing the hydrogen peroxide solution in a flow adding manner, adding into a circulating operation to make the liquid level exceed more than 30cm of the crude product, and circulating well (if the alkali solution barrel is not full of water after pumping, adding clear water to full of water), and starting circulation.
2) And (3) first circulation: controlling the temperature of the solution to be 75 ℃, circulating the solution under the alkali liquor in the barrel by using a pump for 5 hours, then soaking the solution for 0.5 hour, and taking a water sample to detect the concentration of the sodium bicarbonate solution.
3) And (3) second circulation: controlling the temperature of the solution to be 75 ℃, circulating the solution under the alkali liquor in the barrel by using a pump for 1 hour, then soaking for 0.5 hour, and taking a water sample to detect the concentration of the sodium bicarbonate solution.
4) And (3) third circulation: temperature controlAnd (3) circulating for 5 hours at 75 ℃, sampling (crude product), measuring the pH value, and determining that the pH value is 7 and the finished product is qualified (the pH value of the finished product is 5-7). If the product is not qualified, the circulation is continued (the temperature is controlled to be 75 ℃), and the pH value of the crude product and NaHCO in the alkali circulation liquid are determined 3 Adding sodium bicarbonate in appropriate amount until the pH value is qualified. And after the water is drained completely, finishing rinsing.
5) If the pH of the crude manganese dioxide is unqualified after the neutralization circulation, alkali is supplemented or acid water is used for reverse neutralization according to actual conditions, and the temperature is controlled at 75 ℃.
3. Powdering: electrolytic manganese dioxide was ground to 200 mesh powder using a Raymond mill.
4. Deeply removing impurities: rinsing the powdered manganese dioxide powder in hot water at the temperature of 80 ℃, and deeply removing impurity iron brought in during grinding. When the powder is washed by hot water at 80 ℃, acid in the powder is washed into water, and at the moment, the water is acidic and can dissolve simple substance iron, so that the iron removal effect is achieved.
5. And (5) mixing materials in a mixing bin by gravity to obtain a finished product, and packaging and leaving a factory.
The main indicators of the product obtained in this example are shown in table 3:
TABLE 3 product quality situation Table
The foregoing description of specific exemplary embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A post-treatment impurity removal method of electrolytic manganese dioxide for an alkaline manganese battery is characterized in that manganese ore powder, pyrite and dilute sulfuric acid are mixed, reacted and leached, and a crude electrolytic manganese dioxide product is obtained after purification and electrolysis treatment; the method for post-treatment impurity removal of crude manganese dioxide comprises the following steps:
(1) and (3) rinsing the crude product for the first time: firstly, rinsing the crude electrolytic manganese dioxide with hot water at the temperature of 75-95 ℃ for multiple times, and rinsing for one section until the mass concentration of sulfuric acid in a water sample is less than 0.1%;
(2) and (4) second-stage rinsing: taking alkali liquor as neutralization solution and adding hydrogen peroxide solution to carry out multiple cyclic neutralization reactions, and carrying out two-stage rinsing on manganese dioxide powder, wherein the neutralization reaction time is 3-8 h/time, the neutralization temperature is 75-95 ℃, and the neutralization reaction is rinsed until the pH value of crude manganese dioxide is 5-7;
(3) pulverizing, removing impurities, and mixing to obtain the final product.
2. The method for post-treatment impurity removal of electrolytic manganese dioxide for alkaline manganese batteries according to claim 1, wherein the first rinsing in step (1) is:
1) acid washing for the first time: after adding the crude product and hot water into a rinsing barrel, circulating the water in the barrel from bottom to top by using a pump for 1-5 hours, and draining;
2) performing secondary acid washing, namely after hot water is fed into a rinsing barrel, circulating the water in the barrel up and down by using a pump for 1-5 hours, detecting the sulfuric acid content of a water sample, and draining;
3) and (3) if the mass concentration of the sulfuric acid in the water sample is more than or equal to 1%, continuously repeating the acid washing in the step 2) until the mass concentration of the sulfuric acid in the water sample is less than 1%, and performing the following steps.
3. The method for post-treatment impurity removal of electrolytic manganese dioxide for the alkaline-manganese battery according to claim 1, wherein the alkali liquor is a sodium bicarbonate solution with a mass concentration of 1-10%.
4. The method for post-treatment impurity removal of electrolytic manganese dioxide for alkaline manganese batteries according to claim 1, wherein in the second rinsing in step (2), the concentration of the hydrogen peroxide solution is 50-500 ppm.
5. The method for post-treatment impurity removal of electrolytic manganese dioxide for alkaline manganese batteries according to claim 1, wherein the second rinsing in step (2) is:
1) and (3) first circulation: adding alkali liquor and hydrogen peroxide solution into a rinsing barrel, controlling the temperature of the solution to be 75-95 ℃, circulating under the alkali liquor in the barrel by using a pump for 2-4 hours, then soaking for 0.5-2 hours, and taking a water sample to detect the concentration of the alkali liquor;
2) and (3) second circulation: adding alkali liquor and hydrogen peroxide solution into a rinsing barrel, controlling the solution temperature at 75-95 ℃, circulating the solution under the alkali liquor in the barrel for 2-4h by using a pump, then soaking for 0.5-2h, and taking a water sample to detect the concentration of the alkali liquor;
3) taking manganese dioxide test powder, if the pH value reaches 5-7, stopping circulating alkali washing; if not, continuing to cycle step 2).
6. The method for post-treatment impurity removal of electrolytic manganese dioxide for alkaline manganese batteries according to claim 5, wherein after neutralization and rinsing in step 3), appropriate amount of alkali is supplemented or acid water is used for neutralization according to the pH value of the crude product and the concentration of sodium bicarbonate in the alkali circulating liquid until the pH value is qualified, and rinsing is finished after water is drained off.
7. The method for post-treatment impurity removal of electrolytic manganese dioxide for alkaline manganese batteries according to claim 1, wherein the leaching is: mixing and reacting manganese ore powder, pyrite powder and dilute sulfuric acid at the temperature of 90-100 ℃, the pH value of a reaction solution is 1-3.5, and the reaction time is 3-6h, wherein the mixing ratio of the manganese ore powder, the pyrite powder and the dilute sulfuric acid is 1-5: 1: 1-5, and the liquid-solid ratio is 8-20: 1.
8. The method for post-treatment impurity removal of electrolytic manganese dioxide for alkaline manganese batteries according to claim 1, wherein the purification is: adding calcium carbonate into the manganese sulfate solution obtained by leaching, adjusting the pH value of the solution to 3-7, keeping the solution at the temperature of 30-80 ℃ for 0.5-3h, then adding barium sulfide, keeping the solution for 0.5-3h, and performing solid-liquid separation by pressure filtration to obtain the manganese sulfate solution without impurity ions, wherein the impurity ions are qualitative ions without iron and copper.
9. The method for post-treatment impurity removal of electrolytic manganese dioxide for alkaline manganese batteries according to claim 1, wherein a manganese sulfate solution is sent to an electrolytic cell for electrolysis to obtain a crude electrolytic manganese dioxide; the electrolysis conditions were: the concentration of the manganese sulfate solution is 0.5-0.7mol/L, and the current density is 50-120A/m 2 The concentration of the sulfuric acid in the electrolyte is 0.5-0.6mol/L, and the electrolysis period is 8-12 days.
10. The method for post-treatment removal of electrolytic manganese dioxide for alkaline manganese batteries according to claim 1, wherein the powdered manganese dioxide is rinsed in hot water at a temperature of 75-95 ℃ to deeply remove iron impurities brought in during the milling.
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